Photographic filter and antihalation layers containing a silver salt of an azanol dye



Feb. 7, 1950 A. w. ANISH ETAL 2,495,341

PHOTOGRAPHIC FILTER AND ANTIHALATION LAYERS CONTAINING A SILVER SALT OF AN AZANOL DYE Original Filed Aug. 9, 1946 EMULS/ION. 2 cELA7 /v F/L TER LAYER a //7 CONTAW/NG A SILVER w W su/=P0Rr FIG. 1

EMULSION 2--\-\\\\\\\\\\\\ supponr j GELAT/N ANTI-HALAT/ON 1 LAYER CONTAINING A 3F7L//////////// SILVERSALTOFAN AZANOL DYE FIG. 2

INVENTORS ALFRED w. AN/SH LEE c. HENSLEY V ATTO NEY-S Patented Feb. 7, 1950 PHOTOGRAPHIC FILTER AND ANTII-IALA- TION LAYERS CONTAINING A SILVER SALT OF AN AZANOL DYE Alfred W. Anish, Raiford Manor, and Lee C.

Hensley, Binghamton, N. Y., assignors to General Aniline & Film ,Corporation, New York, N. Y., a corporation of Delaware Original application August 9, 1946, Serial No. 689,503. Divided and this application October 5, 1946, Serial No. 701,424

7 Claims.

This invention relates to filter and antihalation dyes for light-sensitive photographic elements, and particularly to silver salts of azanol dyes as photographic filter and anti-halation dyes.

sensitizing dyes, comprising two heterocyclic nitrogenous nuclei linked by a chain of atoms including one or more nitrogen atoms, are known. These dyes are prepared by condensing a quaternary cyclammonium' cyanine dye intermedi ate, containing an active group in the alpha or gamma position, with a diamine, such as, for example, hydrazine, ethylene diamine, p-phenylene diamine, and the like. These condensation products are, for the most. part, insoluble in aqueous solutions of inorganic bases and do not form metal salts with such bases. Moreover,

these products are incapable of forming heavy metal salts.

We have discovered that by condensing a 5- or 6-membered keto-heterocyclic compound, con taining a reactive group, with an aliphatic, aromatic or heterocyclic diamine while heating in the presence of an alcohol as a solvent-diluent with or without a tertiary base, new dyes are obtained which are not only soluble in aqueous solutions of inorganic bases, but also form stable heavy metal salts, particularly silver salts. The silver salts are non-diffusing and readily dischargeable in the usual processing baths. These properties not only make the dyes valuable as sensitizing dyes, but also as filter and anti-halation dyes for silver-halide emulsions.

Accordingly, therefore, it is' an object of the present invention to provide a new class of azanol dyes in the form of their silver salts as filter and anti-halation dyes for light-sensitive photographic elements.

Another object is to provide compounds which form non-diffusing silver salts readily dischargea'cle in the usual processing baths.

A further object is to provide filter and antihalation dyes which have no deleterious effect on the photographic properties of the film.

A still further object is to provide dyes of the azanol'typ as'filter and anti-halation dyes in the form of their silver salts.

Other objects and advantages of this invencomplete a 5-membered or 6-membered heterocyclic nucleus, e. g., of a barbituric acid, a thiobarbituric acid, a rhodanine, an oxazoledione, a thiazolone, a pyrazolone, a hydantoin, a thiohydantoin, and the like, 11. represents a-positive odd integer not greater than 3, and N- XN is the radical of a primary diamine, said diamine being hydrazine, an aliphatic,aromatic, or heterocyclic diamine containing not more than 14 carbon atoms. For instance, when the primary diamine is aromatic, the compounds have thefollowing structure:

C(CH=),.=NAr-N=(CH=),,C

4 1 i \COH Ho o wherein Ar represents an aromatic radical containing up to 12 carbon atoms.

The process of preparing the above azanol dyes comprises heatin ,'preferably under reflux conditions, with or without a tertiarybasa'an alcoholic solution of hydrazine, or an aliphatic, aromatic or heterocyclic diamine with a 5-membered or 6-membered heterocyclic intermediate derived from a barbituric acid, a thio-barbituric acid, a'rhodanine, a hydantoin a thiohydantoin, an oxazoledione, a thiazolone,'a hyrazolone, and the like, having a reactive acetanilido group linked to a carbon'atom of a monoor'polymethine chain of not more than3 carbon atoms adjacent to a keto group of such intermediate.

The diamines used in the preparation of the new dyes of the present invention, and having the general formula:

wherein N-X-N has the same significance as above, are the following:

Hydrazine Ethylenediamine oand p-Phenylenediamine 1.5-naphthylenediamine 2:2-, 2:4'-, and 4.:4-diaminostilbene 4,4'-diamino-3,3'-dichlorophenylmethane 4,4-diamino-benzophenone 4,4 diamino 3,3 dimethoxydiphenylmethane p-p'-Diamino-diphenylmethane 2,6-diamino-pyridine 2,5-diamino-thiodiazole ZA-diamino-quinoline ZA-diamino-B-thio-3,5 thiadiazine The 5-membered heterocyclic intermediates derived from a rhodanine, a thiazolone, a hydantoin, anoxazoledione and a pyrazolone are described in United States Patent 2,186,608 and represented by the general formula:

by this general formula reference is made to:.

4 ('7 acetanilidoallylidene) 1 (2) benzo thiazolyl 3 methyl 5 pyrazolone 4 acetanilidomethylene 3 methyl 1 phen yl 5 pyrazolone 4 ('y acetanilidoallylidene) 3 methyl 1 phenyl-5-pyrazolone 4 acetanilidomethylene 3 methyl 1 (2) pyridyl-B-pyrazolone I 3 acetanilidomethylene 5 methyl thiophen 2-one 5 acetanilidomethylene 3 allylrhodanine 5-acetanilidopropanylidene-3-allylrhodanine 5-acetanilidomethylene 3-phenylrhodanine 5-acetanflidomethylene-3-ethy1rhodanine 5 acetanilidomethylene 3 ethyl 2 thio 2,4(3,5) -oxazoledione 5 ('y acetanilidoallylidene) 2 diphenyl amino 4(5) thiazolone 5 ('y acetanilidoallylidene) 3 ethyl 2 thio-2,4(3,5) -oxazoledione 5 ('y acetanilidoallylidene) 3 ethyl 1 phenyl-Z-thiohydantoin 5 (5 acetanilido AM- pentadienylidene) 3-ethylrhodanine 5 (v acetanilidoallylidene) 2,4,6 triketo hexahydropyrimidine 5 ('y acetanilidoallylidene) 2 thio 4,6

diketohexahydropyrimidine,

and the like.

As solvent-diluents employed in the preparation of the new dyes of the present invention, the following alcohols may be employed: methyl, ethyl, propyl, isopropyl, butyl, benzyl, furfuryl alcohol and the like. Triethylamine, tributylamine, and the like are representative of the tertiary bases which we may use.

When 1 mol of a diamine, of the type mentioned above, is condensed with 1 mol of a 5-membered or 6-membered heterocyclic intermediate in the presence of an alcohol, with or without a tertiary base as acatalyst, a reaction occurs which may be written as follows:

The following examples describe in detail the methods for accomplishing the above objects, but it is to be understood that they are inserted merely for the purpose of illustration and are not to be construed as limitative.

EXAMPLE I rs=c (3-011 11 -0 0: s

i C3135 C3115 A mixture of 3.2 grams (0.01 mol) of -acetanilidomethylene-3-allylrhodanine, 0.6 gram (0.005 mol+ of 'p-phenylenediamine, 125 cc. of isopropyl alcohol and 0.5 cc. of triethylamine was refluxed on a steam bath for about 1 hour, during which time the dye separated from the hot alcohol. The mixture was filtered while hot, and the filter residue boiled out twice with cc. portions of methanol. The dye was further purified by dissolving it in N/1-caustic solution, filtering the solution carefully, and precipitating with dilute acetic acid.

The dye sensitized a silver chlorobromide emulsion to 590 m with a maximum at 545 m In a manner similar to that used in the preparation of the dye described in Example I, 0.4 gram of benzidine was reacted with 1.2 grams of 5-acetanilidomethylene 3 allylrhodanine. This dye sensitized a silver chlorobromide emulsion to 570 m with a maximum at 520 m EXAMPLE III SC-CH=N CHz- CH-C-S S :0 C-OH HO- O: S

i w C3135 CzHs By reacting 0.4 gram of p,p'-diamino-diphenylmethane with 1.2 grams of 5-acetanilidomethylene-3-allylrhodanine in isopropyl alcohol, according to the method of Example I, a yellow dye was obtained. This dye sensitized a silver chlorobromide emulsion to 530 mm, with a maximum at 480 m While following the procedure of Example I, 1.0 gram of p-phenylene diamine and 10.0 grams of 3-acetanilidomethylene 5 methyl-thiophen- 2-one were reacted in cc. of isopropyl alcohol in the presence of 1 cc. of triethylamine. The resulting dye sensitized a silver chlorobromide emulsion to 530 m with a maximum at 510 mp.

EXAMPLE V Hie-C OH HO- t-0H.

While following the procedure of Example I, 0.2 gram of benzidine and 1.0 gram of 3-acetanilidomethylene 5 methyl thiophen 2 one were reacted in 15 cc. of isopropyl alcohol in the presence of several drops of triethylamine. The .resulting dye sensitized a silver chlorobromide emulsion to 520 m with a maximum at 480 mp.

EXAMPLE VI HzC-O Ho-o o-om 1.0 gram of 3-acetanilidomethylene-5-methylthiophen 2 one, 0.5 gram of p,p diamino diphenylmethane and 15 cc. of isopropyl alcohol, containing several drops of triethylamine, were heated under reflux for one hour. Theresulting dye sensitized a silver chlorobromide emulsion to 520 m with a maximum at 480 In EXAMPLE VII Three grams of 4 -1 acetanilidomethylene l phenyl-3-methyl-5 pyrazolone and 0.5 gram of p-phenylenediamine were reacted together in '70 cc. of isopropyl'alcohol in the presence of a few drops of triethylamine. The resulting dye sensitized a silver chlorobromide emulsion to 520 m ll, with a maximum at 470 m l.

' EXAMPLE VIII CuHs 1.0 gram of p-phenylenediamine and 4.0 grams of 5 acetanilidomethylene 3 phenyl 2,4 thiazoledione were reacted in 150 cc. of isopropyl alcohol in thepresence ofxl cc. of triethylamine. The "resulting dye sensitized a silver chlorobromide'emu-lsion to 530' m with a maximum at 510 mu.

1.0 gram of p-phenylenediamine and 4.0 grams of 5 acetanilidomethylene 3 phenyl 2,4 thiazoledione were reacted in 150 cc. of isopropyl alcohol in the presence of 1 cc. of triethylamine. The resulting dye sensitized a silver chlorobromide emulsion to 530 m with a maximum at 510 m a aHE 10 mixture refluxed for 1 hour.

Six grams each of 5-acetanilidomethylene-3- allylrhodanine and ethylene diamine were dissolved in 250 cc. of isopropyl alcohol, and the During this time, a yellow solid separated. After cooling, the reaction mixture was filtered off and the dye recrystallized from methanol. The dye sensitized a silver chlorobromide emulsion to 480 m with a maximum at 440 mp The dye sensitized a silver chlorohromide emulsion to 470 m l, with a maximum at 430 m EXAMPLE XII 0,115 A mixture of 4.4 grams of 5-( -acetanilidoallylidene) 2 diphenylamino 3 ethyl 4(5) thiazolone, 1.0 gram of p-phenylenediamine, 125 cc. of isopropyl alcohol and 0.5 cc. of triethyl- 5 amine were refluxed on a steam bath for about 1 hour, during which time the dye separated from the hot alcohol. The mixture was filtered while hot and the filter residue boiled out twice with 100 cc. portions of methanol. The dye was further purified by dissolving it in N/l-caustic solution, filtering the solution carefully and precipitating with dilute acetic acid.

3.0 grams of S-(acetanilidomethylene) -3-ethy1- 2-thio-2,4(3,5)-oxazoledione, and 1.1 grams of 2,6-diamino-pyridine were mixed with 20 cc. of

isopropyl alcohol containing 1 cc. of triethyl-- amine. The mixture was boiled, under reflux, for 1 /2 hours, cooled and then diluted with 15 cc. of water. The dye which separated was boiled out twice with ethyl alcohol and then dried.

EXAMPLE XIV Three grams of -acetanilidoallylidene)-3- ethyl-l-phenyl-2-thiohydantoin and 1.0 gram of p-phenylenediamine were dissolved in 70 cc. of isopropyl alcohol, containing about 1 cc. of triethylamine, and the mixture heated under reflux for about 1 hour. After cooling to room temperature, the mixture was filtered and the residue boiled out twice with 100 cc. of methanol.

EXAMPLE XV A mixture of 3.0 grams of 5-('y-acetanilidoal lylidene) -2,4,6 triketohexahydropyrimidine, 0.5 gram of an 85% aqueous solution of hydrazine hydrate and 50 cc. of isopropyl alcohol, containing 1 drop of triethylamine, were refluxed for 1 hour. After cooling to room temperature, the solid product which separated out was segregated from the supernatant liquid by decantation. The solid was boiled out twic with 95% methyl alcohol and then dried.

A mixture of 3.1 grams of 5(- -acetanilidoallylidene)-2-thio 4,6-diketohexahydropyrimidine, 1.0 gram of p-phenylenediamine and 50 cc. of isopropyl alcohol and 1 drop of triethylamine were refluxed for 1 hour. The solid which precipitated was filtered 01f and boiled with several portions of methanol.

In the preparation of emulsions containing these azanol dyes, the dye may be dissolved in methyl or ethyl alcohol, and a volume of this solution containing from 5 to 50 milligrams added to a liter of emulsion.

It will be understood that wherein the claims appended hereto the term filter layer is used, that such is intended to include anti-halation layers. While in general practice it may not be necessary to add the dye in amounts larger than those above given, generally, for satisfactory results, amounts usually ranging from 5 to 25 milligrams are sufiicient to obtain the maximum sensitizing effect. However, we do not Wish to limit our invention to the quantities just indicated as the most suitable amount will be found, in each case, by a few comparative experiments. The dyes may be added to the emulsion in the form of solutions, Suitable solvents as indicated in the examples are the alcohols, for instance, methyl or ethyl alcohol which may be anhydrous or diluted with a small volume of water. In actual practice, the dyes are applied to the emulsion during any stage of its production, however, they are preferably added to the finished emulsion before being cast.

The above examples are illustrative only, and should not be construed as limiting the invention, since it will be apparent to those skilled in the art that the dyes of the present invention may be incorporated into photographic emulsions by methods other than those described herein.

The dyes of this invention are further characterized by their ability to form insoluble heavy metal salts, e. g., silver, lead and mercury salts, due to the presence of a salt-forming hydroxyl group. Thus, for example in the presence of silver ions, insoluble silver salts are formed. These silver salts, moreover, are soluble in photographic processing baths, such as sodium thiosulfate. Accordingly, the dyes of this invention are readily applicable as non-diifusing photographic filter and anti-halation dyes in photographic materials in the form of their silver salts. The dyes may be incorporated directly into the photographic emulsion, or applied in a known manner underneath the emulsion layer, intermediate layer between the support and emulsion, as a backing layer on the rear surface of the emulsion support, or as an interlayer between the two emulsion layers.

In the accompanying drawing, the two figures are enlarged section views of photographic elements having filter layers and anti-halation layers made in accordance with the present invention.

Figure 1 represents an embodiment of the invention in which the filter layer is interposed between the emulsion and support.

Figure 2 represents an embodiment in which the anti-halation layer is in the form of a back- In Figures 1 and 2, I is the support, 2 the light sensitive silver halide emulsion layer, and 3 the gelatin filter or anti-halation layer.

The following examples illustrate the use of the dyes of this invention in the form of silver salts as filter and anti-halation agents.

EXAMPLE XVII A photographic filter layer was prepared by mixing the following ingredients to form a Solution B was added to Solution A with rapid stirring. After several minutes, Solution C was added. The silver of the silver nitrate formed a silver salt with the hydroxy group of the dye in the gelatin solution. The final gelatin suspension thus obtained was then coated on a photographic film in the customary manner to serve as a yellow filter layer for blue light absorption. The silver salt of the dye is non-diifusing.

The amount of silver salt used according to the present invention will vary somewhat, depending upon the color desired. In general, an amount more or less than that given in Example XVII may be used for satisfactory results.

For the production of anti-halation coatings, the silver salts of the azanol dyes of the present invention are incorporated into gelatin, treated with silver nitrate, and the dispersions thus obtained are cast in a known manner as coatings underneath the emulsion layer, intermediate layer, between the support and the emulsion or as a backing layer on the rear surface of the emulsion support, or as a support on the emulsion, when the material is intended to be exposed through the support.

ii EXAMPLE XVIII A photographic anti-halation layer was prepared by mixing the following ingredients to form a colored silver salt dispersion in gelatin:

Solution A Compound of Example V grams 7.0 Water cc 200 Sodium hydroxide (4%) cc 7.5 Gelatin (10% solution) cc 100 SolutionB Water cc 100 Silver nitrate grams 3.4

' Solution 0 Gelatin (10% solution) cc 300 Solution B was added to Solution A with rapid stirring. After several minutes, solution C was added. The final gelatin suspension of the silver salt thus obtained was coated on a support in the customary manner as an anti-halation layer.

The filter and anti-halo coatings prepared as described above have been found to have particularly good filter and anti-halant properties and to have no effect on the normal keeping properties of the light-sensitive layer.

This application is a division of our co-pending application Serial No. 689,503 filed on August 9, 1946.

While the present invention has been described in considerable detail with reference to certain preferred procedures, materials and uses, it is understood that the new class of azanol dyes and their use as sensitizing, filter and antihalation dyes is not limited thereto, and that numerous variations and modifications described in the foregoing specification may be made as, for example, the dyes which contain a ketoheterocyclic nucleus, e. g., oxazoledione, hydantoin, and rhodanine nucleus, as illustrated in Examples l-3, 8-10, and 13-15 inclusive, may be further treated with a quaternizing compound such as methyl iodide. pound is then condensed under refiux conditions with a cyclammonium base or salt usual in cyanine dyes, such as N-methyl-2-methylbenzthiazole, having a reactive methyl group in the alpha-position to the nitrogen atom in the presence of a condensing agent such as pyridine, quinoline and the like. In the first reaction (alkylation), the azanol dye is modified to the extent that the nitrogen atom in the 3-position of the oxazoledione, hydantoin or rhodanine ring is quaternized and the sulfur atom in the 2-position is converted to a thioether group. In the second reaction (condensation), the alkylated azanol dye is condensed with a cyclammonium base or salt whereby new compounds, which are also useful as sensitizers, filter and anti-halation 10 wherein =N-X-N'= and n have the same values as above. R1 represents an alkyl, alkylene oraryl radical, R2 represents alkyl, P and Q. which may be the same or different, represent the atoms necessary to complete a heterocyclic ring system of the type usual in cyanine dyes, e. g., indolenines, lepidines, oxazoles, oxazolines, selenazo'les, selenazolines, pyridine, quinoline, thiazoles, thiazolines, diazoles and quinazolines and the corresponding polycyclic compounds, such as benzthiazoles, benzselenazoles, naphthothiazoles, naphthoselenazoles, diazines and the like, Y represents 0, S, or N-C6H5, and Z represents a dye-precipitating acid radical of the type usual in cyanine dyes.

We'claim:

1. A photographic light sensitive element which comprises a support, a gelatino silverhalide emulsion and a filter layer containing a silver salt having the general formula:

wherein A represents the atoms necessary to complete a member selected from the class consisting of a 5-membered and G-membered heterocyclic ring system, n represents a positive odd integer of from 1 to 3, and N-X-N is a radical of an amine containing two primary amino groups of not more than 14 carbon atoms and selected from the class consisting of hydrazine, aliphatic, aromatic and heterocyclic primary diamines.

2. A photographic light sensitive element which comprises a support, a gelatino silverhalide emulsion and a filter layer containing a silver salt having the general formula:

wherein A represents the atoms necessary to The quaternized comcomplete a member selected from the class consisting of a 5-membered and G-membered heterocyclic ring system, it represents a positive odd integer of from 1 to 3, and Ar represents an aromatic radical containing up to 12 nuclear carbon atoms.

3. A photographic light sensitive element which comprises a support, a gelatino silverhalide emulsion and a filter layer containing a silver salt as defined in claim 2, wherein Ar is phenyl.

4. A photographic light sensitive element which comprises a support, a gelatino silverhalide emulsion and a filter layer containing a m silver salt having the general formula:

11 wherein A represents the atoms necessary to complete a member selected from the class consisting of a 5-membered and G-membered heterocyclic ring system, and. n represents a positive odd integer of from 1 to 3.

5. A photographic light sensitive element which comprises a support, a gelatino silverhalide emulsion and a filter layer containing a silver salt corresponding to the formula:

6. A photographic light sensitive element which comprises a support, a gelatlno silverhalide emulsion and a filter layer containing a silver salt corresponding to the formula:

( liH (13135 12 7. A photographic light sensitive element which comprises a support, a gelatino silverhalide emulsion and a filter layer containing a silver salt corresponding to the formula:

l l 5 s=0 C-QAg AgO- =s N 10 Ja a hHs ALFRED W. ANISH. LEE C. HENSLEY.

REFERENCES CITED 15 The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,155,475 Dieterle Apr. 25, 1939 2,166,736 White et al. July 18, 1939 2,312,153 Dieterle Feb. 23, 1943 2,340,882 Kendall Feb. 8, 1944 FOREIGN PATENTS Number Country Date 542,905 Great Britain Feb. 2, 1942 

1. A PHOTOGRAPHIC LIGHT SENSITIVE ELEMENT WHICH COMPRISES A SUPPORT, A GELATINO SILVERHALIDE EMULSION AND A FILTER LAYER CONTAINING A SILVER SALT HAVING THE GENERAL FORMULA: 